Adsorption and desorption of hydrogen by gas-phase Pd clusters, Pd-n(+), were investigated by thermal desorption spectroscopy (TDS) experiments and density functional theory (DFT) calculations. The desorption processes were examined by heating the clusters that had adsorbed hydrogen at room temperature. The clusters remaining after heating were monitored by mass spectrometry as a function of temperature up to 1000 K, and the temperature-programmed desorption (TPD) curve was obtained for each Pd-n(+). It was found that hydrogen molecules were released from the clusters into the gas phase with increasing temperature until bare Pd-n(+) was formed. The threshold energy for desorption, estimated from the TPD curve, was compared to the desorption energy calculated by using DFT, indicating that smaller Pd-n(+) clusters (n <= 6) tended to have weakly adsorbed hydrogen molecules, whereas larger Pd-n(+) clusters (n >= 7) had dissociatively adsorbed hydrogen atoms on the surface. Highly likely, the nonmetallic nature of the small Pd clusters prevents hydrogen molecule from adsorbing dissociatively on the surface.